N-substituted-3-[(2,3-dimethylmaleimido)amino)]-benzenesulfonamide derivatives, hebicidal compositions and method of use

ABSTRACT

Disclosed herein are N-substituted-3-[(2,3-dimethylmaleimido) amino]benzenesulfonamide derivatives of the formula (I): ##STR1## wherein R is Cl, C 1  -C 3  alkyl or C 1  -C 4  alkoxycarbonyl; Z is CH or N; X 1  is Cl or C 1  -C 3  alkoxy; and X 2  is C 1  -C 3  alkyl or C 1  -C 3  alkoxyl, a process for the preparation thereof, and herbicidal compositions containing the N-substituted-3-[(2,3-dimethylmaleimido) amino]benzenesulfonamide derivatives as active ingredients.

BACKGROUND OF THE INVENTION

1) Field of the Invention

The present invention relates toN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivatives, a preparation process thereof, and herbicidal compositionscontaining the derivatives as active ingredients.

2) Description of the Related Art

Numerous compounds have heretofore been proposed as herbicides.Regarding N-substituted benzenesulfonamide derivatives, a variety ofcompounds has also been reported as herbicides.

For example, EP-A-116518 and Japanese Patent Application Laid-Open(KOKAI) No. 129276/1987 disclose the use ofN-(phenylsulfonyl)-N'-pyrimidyl- or triazinyl urea derivatives, whichhave one or more substituents on the phenyl nucleus, as herbicides.Illustrative of the substituent on the 3-position of the phenyl nucleusinclude various groups such as NHCH₃, OCH₂ CF₃ and SCH₂ CF₃.

There have conventionally been strong demands for herbicides capable ofexhibiting reliable herbicidal activity even at such low applicationdosages as bringing about the advantage of reducing the amount presentin the environment, herbicides capable of exhibiting selectivity betweencrops and weeds irrespective of variations in environmental conditions,herbicides free from crop injury to the second crop in double cropping,etc. The present invention has been completed with a view toward meetingsuch demands.

The present inventors have found, as a result of an investigation, thata series of compounds still unreported in any publications known to theinventors and having a chemical structure different from the compoundsdisclosed in EP-A-116518 and Japanese Patent Application Laid-Open(KOKAI) No. 129276/1987 referred to above.

SUMMARY OF THE INVENTION

Therefore, an object of the invention is to provide novel compoundswhich show excellent herbicidal activity.

Another object of the invention is to provide a process for preparingnovel compounds which show excellent herbicidal activity.

A further object of the invention is to provide intermediates useful inthe preparation of novel compounds which show excellent herbicidalactivity.

A still further object of the invention is to provide novel herbicidalcompositions which show excellent herbicidal activity.

A still further object of the invention is to provide a method forcontrolling monocotyledonous or dicotyledonous weeds on an agriculturalor nonagricultural land.

In one aspect of the invention, there is thus provided AnN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivative of the formula (I): ##STR2## wherein R is C1, C₁ -C₃ alkyl orC₁ -C₄ alkoxycarbonyl; Z is CH or N; X¹ is C1 or C₁ -C₃ alkoxyl; and X²is C₁ -C₃ alkyl or C₁ -C₃ alkoxyl.

In another aspect of the invention, there is also provided a process forthe preparation of anN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivative of claim 1, which comprises reacting a3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide derivative of theformula (II): ##STR3## wherein R is C1, C₁ -C₃ alkyl or C₁ -C₃alkoxycarbonyl, with a phenylcarbamate derivative of the followingformula (III): ##STR4## wherein Z is CH or N, X¹ is C1 or C₁ -C₃alkoxyl, and X² is C₁ -C₃ alkyl or C₁ -C₃ alkoxyl.

In a further aspect of the invention, there is also provided a3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide derivative useful asan intermediate in the preparation of the aboveN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide, whichis represented by the following formula (II).

In a still further aspect of the invention, there is also provided aherbicidal composition comprising a herbicidally effective amount of anN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivative of the formula (I) and an agronomically-acceptable vehicle ordiluent.

In a still further aspect of the invention, there is also provided amethod for the control of monocotyledonous or dicotyledonous weeds on anagricultural or nonagricultural land, which comprises applying to theagricultural or non-agricultural land theN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivative of the formula (I) or a herbicidal composition comprisingsaid derivative.

The N-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivatives of the present invention, which are represented by theformula (I), exhibit reliable herbicidal activity at low applicationdosages and show selectivity between crops and weeds. The herbicidalcompositions of the invention, which contain the above derivatives aseffective ingredients, are suitable particularly for controlling beforeor after germination dicotyledonous and/or monocotyledonous weeds inimportant crops, for example, such as wheat, rice, corn, soybean,cotton, beet, potato, tomato or the like. They are also usable for thecontrol of weeds not only on agricultural lands such as upland fields,paddy fields and orchards but also on non-agricultural lands such asathletic fields and factory sites.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Specific examples of theN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivative represented by the formula (I) in the invention include thoseshown in Table 1.

                  TABLE 1                                                         ______________________________________                                         ##STR5##                                                                     Compound                                                                      No.        R          X.sup.1  X.sup.2                                                                              Z                                       ______________________________________                                        I-1        Cl         OCH.sub.3                                                                              OCH.sub.3                                                                            CH                                      I-2        CH.sub.3   OCH.sub.3                                                                              OCH.sub.3                                                                            CH                                      I-3        COOCH.sub.3                                                                              OCH.sub.3                                                                              OCH.sub.3                                                                            CH                                      I-4        COOC.sub.2 H.sub.5                                                                       OCH.sub.3                                                                              OCH.sub.3                                                                            CH                                      I-5        COOCH.sub.3                                                                              OCH.sub.3                                                                              CH.sub.3                                                                             N                                       I-6        COOC.sub.2 H.sub.5                                                                       OCH.sub.3                                                                              CH.sub.3                                                                             N                                       I-7        COOCH.sub.3                                                                              OCH.sub.3                                                                              OCH.sub.3                                                                            N                                       I-8        COOC.sub.2 H.sub.5                                                                       Cl       OCH.sub.3                                                                            CH                                      ______________________________________                                    

The N-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivatives represented by the formula (I) can each be synthesized byreacting a 3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide derivativeof the formula (II) and a phenylcarbamate derivative of the followingformula (III) in the presence of a base and in an organic solvent inaccordance with the following reaction formula: ##STR6## wherein R, Z,X¹ and X² have the same meanings as defined above.

In the above reaction, dimethylacetamide, N-methylpyrrolidone,acetonitrile or the like can be used as an organic solvent. On the otherhand, diazabicyclooctane, diazabicyclononene, diazabicycloundecene orthe like can be used as a base.

The reaction is conducted at a temperature in a range of from -20° C. to100° C., preferably from 0° C. to 50° C. for a reaction period in arange of from 0.5 hour to 24 hours.

After completion of the reaction, the reaction mixture is added to anaqueous solution of dilute hydrochloric acid and the precipitate thusformed is collected by filtration. The precipitate is dried in air andthen purified by a purification technique such as reprecipitation orcolumn chromatography or by a washing technique, whereby the intendedN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivative represented by the formula (I) can be obtained with highpurity.

The 3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide derivativerepresented by the formula (II), which is a preparation intermediate andis employed as the starting material in the above reaction, can besynthesized in accordance with the following reaction formula, using asa starting material a 3-aminobenzenesulfonamide derivative representedby the following formula (IV): ##STR7## wherein R has the same meaningas defined above.

Synthesis of the 3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivative represented by the formula (II) can be practiced in thefollowing manner. A 3-hydrazinobenzenesulfonamide derivative representedby the formula (V), which has been obtained by diazotizing the aminogroup of the compound represented by the formula (IV) and reducing thethus-diazotized derivative, and 2,3-dimethylmaleic anhydride are stirredat 30°-120° C., preferably 70°-90° C. for 0.5-4 hours in acetic acid orpropionic acid. After completion of the reaction, the reaction mixtureis evaporated to dryness under reduced pressure and the resulting crudeproduct is purified by column chromatography, whereby the3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide derivativerepresented by the general formula (II) can be obtained with goodpurity.

The compound represented by the formula (IV), which was used in theabove reaction formula, can be obtained from the correspondingnitrobenzene derivative, for example, by using the process described inBull. Chem. Soc. Jpn., 55, 3824 (1982); or from the corresponding3-nitroaniline derivatives, for example, by the process described inChem. Ber., 90, 841 (1957) or J. Macromol. Sci. Chem., 1969, 941,namely, by synthesizing 3-nitrobenzenesulfonamide derivatives and thenreducing the nitro groups into amino groups with SnCl₂ in methanol orethanol containing 35% hydrochloric acid.

Specific examples of the3-[(2,3-dimethylmaleimido)amino]benzenesulfonamide derivativerepresented by the formula (II) and useful as a preparation intermediateare summarized in Table 2.

In addition, specific examples of the compound represented by theformula (V) are shown in Table 3.

                  TABLE 2                                                         ______________________________________                                         ##STR8##                                                                     Compound                                                                      No.                  R                                                        ______________________________________                                        II-1                 Cl                                                       II-2                 CH.sub.3                                                 II-3                 COOCH.sub.3                                              II-4                 COOC.sub.2 H.sub.5                                       ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                         ##STR9##                                                                     Compound                                                                      No.                  R                                                        ______________________________________                                        V-1                  H                                                        V-2                  Cl                                                       V-3                  CH.sub.3                                                 V-4                  COOCH.sub.3                                              V-5                  COOC.sub.2 H.sub.5                                       ______________________________________                                    

Further, the compound represented by the formula (III) can be obtainedfrom phenyl chloroformate and the corresponding2-amino-4,6-(di-substituted) pyrimidine (or 1,3,5-triazine), forexample, by the process described in European Patent Specification No.238,070.

The N-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivatives exhibit reliable herbicidal activity at low applicationdosages and show selectivity between crops and weeds. The herbicidalcompositions of the invention, which contain the above compounds aseffective ingredients, are therefore suitable for controlling eitherbefore or after emergence monocotyledonous weeds and/or dicotyledonousweeds in important crops such as wheat, rice, corn, soybean, cotton,beet, potato and tomato.

Exemplary dicotyledonous weeds which can be controlled by the herbicidesof the invention include Amaranthus, Bidens, Stellaria, Solanum,Abutilon, Convolvulus, Matricaria, Galium, Lindernia, etc.

Illustrative monocotyledonous weeds include Echinochloa, Setaria,Digitaria, Avena, Cyperus, Alisma, Monochoria, etc.

The herbicides of the invention may take any preparation forms such aswettable powder, emulsion, powder, granule and the like. Knownagronomically-acceptable vehicles (diluents) and aids can be used.

The applicable places of the herbicides according to the invention rangefrom agricultural lands such as upland fields, paddy fields and orchardto non-agricultural lands such as athletic fields and factory sites.

EXAMPLES

The present invention will hereinafter be described by the followingexamples.

SYNTHESIS EXAMPLE 1 Synthesis of ethyl4-(2,5-dihydro-3,4-dimethyl-2,5-dioxo-1H-pyrrol-1-yl)amino]-2-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonylaminosulfonyl]benzoate(Compound No. I-4)

At room temperature, 158 mg (0.43 mmol) of ethyl2-(aminosulfonyl)-4-[(2,5-dihydro-3,4-dimethyl-2,5-dioxo-1H-pyrrol-1-yl)amino]benzoateand 118 mg (0.43 mmol) of phenyl (4,6-dimethoxypyrimidin-2-yl)carbamatewere dissolved in 1.5 ml of N,N-dimethylacetamide. Then, 73 mg of1,8-diazabicyclo[5.4.0]undec-7-ene were added, followed by stirring for5 minutes. The resultant mixture was allowed to stand for 15 hours.Thereafter, 0.2 ml of 35% hydrochloric acid was added to 20 ml of icewater, followed by the addition of the reaction mixture in 0.2 mlportions under stirring. After the reaction mixture was stirred for 20minutes, the resulting precipitate was collected by filtration and driedin air. Using dichloromethane as an eluent, the crude product waspurified by chromatography on a column of silica gel ("WAKO GEL C-300",trade name; product of Wako Pure Chemical Industries, Ltd.). Yield: 162mg (58%). Melting point: 121°-123° C. (decomposed). Its physicochemicalproperties are shown in Table 4.

SYNTHESIS EXAMPLE 2 Synthesis of methyl4-[(2,5-dihydro-3,4-dimethyl-2,5-dioxo-1H-pyrrol-1-yl)amino]-2-(4,6dimethoxy1,3,5-triazin-2-yl)aminocarbonyl]benzoate(Compound No. I-7)

At room temperature, 172 mg (0.5 mmol) of methyl2-(aminosulfonyl)-4-[(2,5-dihydro-3,4-dimethyl-2,5-dioxo-1H-pyrrol-1-yl)amino]benzoateand 138 mg (0.5 mmol) of phenyl(4,6-dimethoxy-1,3,5-triazin-2-yl)carbamate were dissolved in 1.5 ml ofN,N-dimethylacetamide. Then, 76 mg of 1,8-diazabicyclo[5.4.0]undec-7-enewere added, followed by stirring for 5 minutes. The resultant mixturewas allowed to stand for 6 hours. Thereafter, 0.2 ml of 35% hydrochloricacid was added to 20 ml of ice water, followed by the addition of thereaction mixture in 0.2 ml portions under stirring. After the reactionmixture was stirred for 20 minutes, the resulting precipitate wascollected by filtration and dried in air. Using a 1:2 mixed solvent ofmethyl acetate and benzene as an eluent, the crude product was purifiedby chromatography on a column of silica gel ("WAKO GEL C-300", tradename; product of Wako Pure Chemical Industries, Ltd.). Yield: 59 mg(22%). Melting point: 123°-127° C. Its physicochemical properties areshown in Table 4.

The otherN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivatives shown in Table 1 were also synthesized in a similar mannerto Synthesis Example 1. Namely, after obtaining crude products by asimilar procedure to Synthesis Example 1, they were separately purifiedby chromatography on a silica gel column, reprecipitation or washing.Physicochemical properties of each of theN-substituted-3-[(2,3-dimethylmaleimido)-amino]benzenesulfonamidederivatives are shown in Table 4. Incidentally, in Table 4 and Table 6which will be given subsequently, the abbreviations in the columns forNMR data have the following meanings:

δ: (ppm), s: singlet, d: doublet, t: triplet,

q: quartet, m: multiplet, dd: double doublet,

br: broad.

Further, with respect to the individualN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivatives, the solvents employed upon purification thereof and theyields attained were as follows:

Compounds purified by reprecipitation:

    ______________________________________                                        Compound No.                                                                              Solvent employed Yield (%)                                        ______________________________________                                        I-1         CH.sub.2 Cl.sub.2 + petroleum ether                                                            38                                               I-2         CH.sub.2 Cl.sub.2 + petroleum ether                                                            75                                               ______________________________________                                    

Compounds purified by washing:

    ______________________________________                                        Compound No.  Solvent employed                                                                           Yield (%)                                          ______________________________________                                        I-3           petroleum ether                                                                            40                                                 ______________________________________                                    

Compounds purified by column chromatography:

    ______________________________________                                        Compound No.                                                                              Solvent employed Yield (%)                                        ______________________________________                                        I-4         CH.sub.2 Cl.sub.2                                                                              58                                               I-5         methyl acetate + benzene                                                                       22                                               I-6         ethyl acetate + benzene                                                                        21                                               I-7         methyl acetate + benzene                                                                       22                                               I-8         ethyl acetate + benzene                                                                        64                                               ______________________________________                                    

    TABLE 4       Melting Point or MS(m/e) Decomposition Compound No. (A)* (B)** Point     (°C.) IR (KBr, cm.sup.-1) NMR (δ) CDCl.sub.3       I-1 355 155 142-144 3200-2600,1720,1610,1580,1450, 2.006(6H,s)     3.913(6H,s) 5.751(1H,s) 6.234(1H,s) 6.810(1H,dd,8.54Hz,2.44Hz)     Decomposition 1370,1360,1200,1170,590,520 7.218(1H,s) 7.277(1H,d,8.54Hz)     7.665(1H,d,2.44Hz) 12.877(1H,s) I-2 335 155 120-122 3420br,2940,1780,1720     ,1610, 2.040(6H,s) 2.560(3H,s) 3.939(6H,s) 5.780(1H,s) 6.051(1H,s)     Decomposition 1580,1490,1450,1370,1350,1220, 6.846(1H,dd,8Hz,1.5Hz)     7.147(1H,d,8Hz) 7.198(1H,s) 7.645(1H,d,1.5Hz)     1200,1170,590 12.611(1H     ,s) I-3 379 155 136-139 3400-2700br,3300,2940,1780, 2.057(6H,s) 3.822(3H,     s) 4.005(6H,s) 5.773(1H,S) 6.576(1H,s)    Decomposition 1720,1600,1570,14     90,1440,1370, 6.829(1H,dd,8Hz,1.5Hz) 7.367(1H,s) 7.666(1H,d,8Hz)     7.797(1H,d,1.5Hz)     1350,1270,1240,1220,1190,1160, 12.523(1H,s)     1120,1090,1050,820,770,750,     630,580,530,510 I-4 393 155 121-123     3380-2700,3320,1780,1710,1600, 1.318(3H,t,7.33Hz) 2.055(6H,s) 4.011(6H,s)      4.274(2H,q,7.33Hz) 5.768(1H,s)    Decomposition 1570,1490,1440,1350,1270     ,1240, 6.610(1H,s) 6.832(1H,dd,8.55Hz,2.44Hz) 7.384(1H,s) 7.660(1H,d,8.55     Hz)     1220,1190,1170,1120,580 7.792(1H,d,2.44Hz) 12.503(1H,s) I-5 379     140 123-127 3330,3200-2800,1790,1730,1610, 2.052(6H,s) 2.626(3H,s)     3.874(3H,s) 4.088(3H,s) 6.828(1H,dd,8.55Hz,2.44Hz)    Decomposition     1560,1490,1450,1360,1270,1160, 6.881(1H,s) 7.684(1H,d,8.55Hz) 7.797(1H,d,     2.44Hz) 8.145br(1H,s)     1120,820,590 12.405br(1H,s) I-6 393 140     123-126 3330,3200-2800,1790,1730,1610, 1.349(3H,t,7.32Hz) 2.052(6H,s)     2.616(3H,s) 4.084(3H,s) 4.326(2H,q,7.32Hz)    Decomposition 1570,1490,145     0,1370,1270,1250, 6.771(1H,s) 6.830(1H,dd,8.55Hz,2.45Hz) 7.684(1H,d,8.55H     z) 7.782(1H,d,2.45Hz)     1170,820,590 7.995br(1H,s) 12.435br(1H,s) I-7     379 156 123-127 3330,3200-2800,1790,1730,1610, 2.050(6H,s) 3.876(3H,s)     4.101(6H,s) 6.793(1H,s) 6.835(1H,dd,8.55Hz,2.44Hz)    Decomposition     1570,1490,1450,1380,1350,1270, 7.682(1H,d,8.55Hz) 7.789(1H,d,2.44Hz)     8.007(1H,s) 12.120(1H,s)     1240,1170,1150,820,590 I-8 393 159 118-122     3330,3200-2800,1790,1730,1610, 1.335(3H,t,7.33Hz) 2.052(6H,s) 4.135(6H,s)      4.302(2H,q,7.33Hz) 6.469(1H,s)    Decomposition 1590,1570,1500,1450,1360     ,1330, 6.698(1H,s) 6.835(1H,dd,8.55Hz,2.44Hz) 7.682(1H,d,8.55Hz)     7.792(1H,d,2.44Hz)     1270,1250,1170,1120,590 7.797(1H,s) 12.037(1H,s)     *(A)     ##STR10##     **(B)     ##STR11##

SYNTHESIS EXAMPLE 3 Synthesis of preparation intermediate, ethyl2-(aminosulfonyl)4-[(2,5-dihydro-3,4-dimethyl-2,5-dioxo-1H-pyrazol-1-yl)aino]benzoate(Compound No. II4) (1) Synthesis of ethyl2-(aminosulfonyl)4-hydrazinobenzoate (Compound No. V5)

Ethyl 4-amino2-(aminosulfonyl)benzoate (2.44 g; 10 mmol) was finelyground and then added to a mixture of 5 ml of 35% hydrochloric acid and5 ml of water. The mixture thus prepared was stirred for 5 minutes atroom temperature. It was thereafter cooled with ice water and understirring, solution of 0.72 g (10.5 mmol) of sodium nitrite in 3 ml ofwater was added over 3 minutes to conduct diazotization.

In 5 ml of 35% hydrochloric acid, 5.2 g (27.4 mmol) of stannous chloridewere dissolved. The resulting solution was cooled with ice water andstirred, followed by the addition of the diazotized compound preparedabove.

After the resultant mixture was stirred for 20 minutes, it was left overfor 15 hours in a refrigerator. The reaction mixture was thentransferred into a 2-l beaker, to which 28 g of sodium bicarbonatepowder were then added under stirring to adjust the pH to 6. The mixturethus prepared was then extracted twice with 700 ml of ethyl acetate. Theextract was dried over sodium sulfate, and ethyl acetate was distilledoff to obtain a pale brown solid. Yield: 2.66 g (98%). Melting point:122°-124° C. (decomposed). Its physicochemical properties are shown inTable 6.

(2) Synthesis of ethyl2-(aminosulfonyl)4-[(2,5-dihydro-3,4-dimethyl-2,5-dioxo-1H-pyrrol-1-yl)amnobenzoate(Compound No. II4)

The compound synthesized in the above procedure (1) [Compound No. V5;259 mg (1 mmol)] and 132.6 mg (1 mmol) of 2,3-dimethylmaleic anhydridewere dissolved at room temperature in 4 ml of acetic acid, followed bystirrin at 80°-90° C. for 3 hours. The reaction mixture was thenevaporated to dryness under reduced pressure. Using dichloromethane asan eluent, the crude reaction product thus obtained was purified bychromatography on a column of silica gel ("WAKO GEL C300", trade name;product of Wako Pure Chemical Industries, Ltd.). Yield: 203.8 mg (55%).Melting point: 184°-186° C. Its physicochemical properties are shown inTable 5.

In addition, physicochemical properties of the other compounds of theformula (II) synthesized in a similar manner to the abovedescribedprocedure are also shown in Table 5.

Further, physicochemical properties of other preparation intermediatessynthesized in a similar manner to the above procedure (1) are alsoshown in Table 6.

                                      TABLE 5                                     __________________________________________________________________________                    Melting Point                                                 Compound                                                                            Yield                                                                             MS (m/e)                                                                            or Decomposition                                              No.   (%) M+    Point (°C.)                                                                     IR (KBr, cm.sup.-1)                                  __________________________________________________________________________    II-1  67  329   216-221  3370, 3320, 3270, 1780, 1730, 1600,                                           1550, 1470, 1340, 1175, 1165, 590,                   II-2  62  309   109-111  3370, 3320, 3260, 1770, 1710, 1600,                                  Decomposed                                                                             1480, 1320, 1310, 1150, 1130, 1080,                                           1050, 920, 680, 590, 510                             II-3  47  353   120-125  3320br, 2950, 1780, 1720, 1600, 1430,                                         1340, 1310, 1280, 1250, 1170, 1120,                                           1090, 1050, 930, 770, 710, 700, 590,                                          510                                                  II-4  55  367   184-186  3380, 3250, 2980, 1780, 1720, 1700,                                           1600, 1420, 1320, 1290, 1270, 1240,                                           1160, 1130, 1090, 1050, 780, 700, 600,                                        520                                                  __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________                         Melting Point                                            Compound                                                                            Yield                                                                             MS (m/e)   or Decomposition                                         No.   (%) M+         Point (°C.)                                                                     IR (KBr, cm.sup.-1)                                                                          NMR (δ)                    __________________________________________________________________________    V-1   89  187        113-116  3360, 3350, 3300, 3220, 1600,                                                 1470, 1340, 1330, 1290, 1140,                                                 1090, 780, 680, 580, 510                        V-2   84  221        155-158  3370, 3330, 3130, 2970, 1590,                                        Decomposed                                                                             1560, 1460, 1330, 1270, 1160,                                                 970, 830, 740, 690, 590, 550,                                                 510                                             V-3   83  201        161-164  3300, 3250, 3010, 1610, 1490,                                                                d.sub.6 -DMSO:2.409(3H,s)                                      1300, 1160, 1140, 920, 820,                                                                  4.025br(2H,s) 6.840                                            690, 600, 520  (1H,dd,8.5 Hz,1.8 Hz)                                                         6.901(1H,s) 7.048(1H,                                                         d,8.5 Hz) 7.148(2H,s)                                                         7.349(1H,d,1.8 Hz)               V-4   86  245        168-170  3350, 3310, 3250, 1680, 1630,                                                 1590, 1440, 1350, 1330, 1300,                                                 1270, 1170, 1160, 780, 700, 600                 V-5   98  259        122-124  3320, 3270, 2980, 1700, 1590,                                        Decomposed                                                                             1370, 1320, 1300, 1270, 1250,                                                 1150, 1120, 770, 740, 700                       __________________________________________________________________________

Compounds obtained in a similar manner to Synthesis Examples 1 and 2 areshown in Table 7.

                  TABLE 7                                                         ______________________________________                                         ##STR12##                                                                    Compound                                                                      No.        R          X.sup.1  X.sup.2                                                                              Z                                       ______________________________________                                        I-9        COOCH.sub.3                                                                              OCH.sub.3                                                                              OCH.sub.3                                                                            N                                       I-10       Cl         OCH.sub.3                                                                              CH.sub.3                                                                             N                                       I-11       Cl         OCH.sub.3                                                                              OCH.sub.3                                                                            N                                       I-12       CH.sub.3   OCH.sub.3                                                                              CH.sub.3                                                                             N                                       I-13       CH.sub.3   OCH.sub.3                                                                              OCH.sub.3                                                                            N                                       I-14       Cl         OCH.sub.3                                                                              CH.sub.3                                                                             CH                                      I-15       Cl         CH.sub.3 CH.sub.3                                                                             CH                                      I-16       COOCH.sub.3                                                                              OCH.sub.3                                                                              CH.sub.3                                                                             CH                                      I-17       COOCH.sub.3                                                                              CH.sub.3 CH.sub.3                                                                             CH                                      I-18       CH.sub.3   CH.sub.3 CH.sub.3                                                                             CH                                      ______________________________________                                    

Formulation examples and tests will hereinafter be described. It shouldbe borne in mind that the vehicles (diluents) and aids, their mixingratios and effective components can vary in wide ranges, respectively.

Formulation Example 1: Wettable Powder

    ______________________________________                                        Compound (Compound No. I-4)                                                                        50 parts                                                 A salt of ligninsulfonic acid                                                                       5 parts                                                 A salt of alkylsulfonic acid                                                                        3 parts                                                 Diatomaceous earth   42 parts                                                 ______________________________________                                    

The above ingredients are mixed and ground into a wettable powder. Forapplication, it is diluted with water.

Formulation Example 2: Emulsion

    ______________________________________                                        Compound (Compound No. I-5)                                                                        25 parts                                                 Xylene               65 parts                                                 Polyoxyethylene alkylaryl ether                                                                    10 parts                                                 ______________________________________                                    

The above ingredients are mixed intimately into an emulsion. Forapplication, it is diluted with water.

Formulation Example 3: Granule

    ______________________________________                                        Compound (Compound No. I-7)                                                                         8 parts                                                 Bentonite            40 parts                                                 Clay                 45 parts                                                 A salt of ligninsulfonic acid                                                                       7 parts                                                 ______________________________________                                    

The above ingredients are mixed intimately and after the addition ofwater, were kneaded and then formed into granules by an extrudinggranulator. They were then dried to provide a granular formulation,namely, a granule.

Test 1: Test on Herbicidal Activity by Foliar Application

Herbicidal solutions of each test compound, which had been prepared bydissolving at predetermined concentrations such a wettable powder of thetest compound as that described in the above formulation example, andsprayed at dosages of 10 g/ha and 100 g/ha over foliar parts ofAmaranthus retroflexus (Redroot pigweed), Bidens pilosa (Commonblackjack), Sinapis arvensis (Wild mustard), Stellaria media (Commonchickweed), Cassia obtusifolia (Sicklepod), Solanum nigrum (Blacknightshade), Abutilon theophrasti (Velvetleaf), Convolvulus arvensis(Field bindweed), Matricaria chamomilla (Wild chamomile), Setariaviridis (Green foxtail), Echinochloa frumentaceum (Barnyard grass),Avena fatua (Wild oat), and Digitaria adscendens (Henry crabgrass) whichhad been allowed to grow individually to 2-4 leaf stage in pots.Fourteen days later after spraying of the test compound, its herbicidalactivity was evaluated in accordance with the below-described system.The results are summarized in Table 8.

Ranking system:

Herbicidal activity

0: No effects

1: less than 30% of total kill

2: 30% (inclusive)--50% (exclusive) of total kill

3: 50% (inclusive)--70% (exclusive) of total kill

4: 70% (inclusive)--90% (exclusive) of total kill

5: 90% (inclusive)--100% (inclusive) of total kill

                                      TABLE 8                                     __________________________________________________________________________    Compound                                                                            Amount                                                                  No.   (g/ha)                                                                             A.r.                                                                             B.p.                                                                             S.a.                                                                             S.m.                                                                             C.o.                                                                             S.n.                                                                             A.t.                                                                             C.a.                                                                             M.c.                                                                             S.v.                                                                             E.f.                                                                             A.f.                                                                             D.a.                           __________________________________________________________________________    I-1    10  5  3  5  5  3  2  5  1  5  2  2  5  4                                    100  5  5  5  5  5  5  5  5  5  5  5  5  5                              I-2    10  5  3  5  5  4  4  5  2  1  1  1  1  0                                    100  5  5  5  5  5  5  5  3  5  3  3  5  3                              I-3    10  5  3  5  5  1  5  3  3  5  1  2  1  1                                    100  5  5  5  5  5  5  5  5  5  5  5  5  5                              I-4    10  5  5  5  5  5  5  5  5  5  4  2  5  2                                    100  5  5  5  5  5  5  5  5  5  5  5  5  5                              I-5    10  4  5  5  5  1  1  5  3  5  2  1  1  1                                    100  5  5  5  5  5  5  5  4  5  4  4  3  4                              I-6    10  5  5  5  5  2  5  5  4  5  3  3  3  1                                    100  5  5  5  5  4  5  5  5  5  3  5  5  2                              I-7    10  4  4  5  5  2  5  5  3  5  3  2  3  1                                    100  5  5  5  5  5  5  5  5  5  4  5  5  3                              I-8    10  5  4  5  5  3  4  5  4  5  2  2  2  2                                    100  5  5  5  5  4  5  5  5  5  4  4  5  3                              __________________________________________________________________________     (Note)                                                                        A.r.: Amaranthus retroflexus                                                  B.p.: Bidens pilosa                                                           S.a.: Sinapis arvensis                                                        S.m.: Stellaria media                                                         C.o.: Cassia obtusifolia                                                      S.n.: Solanum nigrum                                                          A.t.: Abutilon theophrasti                                                    C.a.: Convolvulus arvensis                                                    M.c.: Matricaria chamomilla                                                   S.v.: Setaria viridis                                                         E.f.: Echinochloa frumentaceum                                                A.f.: Avena fatua                                                             D.a.: Digitaria adscendens                                               

TEST 2: GERMINATION TEST OF SEEDS

Two sheets of filter paper were placed in a superposed relation in eachof Petri dishes having a diameter of 9 cm. Water suspensions of eachtest compound (concentrations of the active ingredient: 1 ppm and 50ppm) were separately poured in an amount of 5 ml per dish into the Petridishes. Seeds of Amaranthus retroflexus (Redroot pigweed), Bidens pilosa(Common blackjack), Matricaria chamomilla (Wild chamomile), Solanumnigrum (Black nightshade), Echinochloa oryzicola (Barnyard grass),Cyperus iria (Rice flatsedge) and Setaria viridis (Green foxtail) wereplaced at a rate of 10 seeds per dish in the Petri dishes. They weretherafter allowed to germinate in a constant-temperature chamber at 28°C. Fourteen days later after placement in the Petri dishes, the degreesof germination and growth inhibition were observed visually. Theobservation results were ranked in accordance with the below-described6-stage system. The results are summarized in Table 9.

Growth inhibition rate

0: No inhibition

1: less than 30%

2: 30% (inclusive)--50% (exclusive)

3: 50% (inclusive)--70% (exclusive)

4: 70% (inclusive)--90% (exclusive)

5: 90% (inclusive)--100% (exclusive)

                  TABLE 9                                                         ______________________________________                                        Com-   Concen-                                                                pound  tration                                                                No.    (ppm)    A.r.   B.p. M.c. S.n. E.o. C.i. S.v.                          ______________________________________                                        I-1     1       3      0    3    3    2    4    2                                    50       4      3    4    3    4    4    4                             I-2     1       4      4    5    3    4    4    5                                    50       4      4    5    4    5    4    5                             I-3     1       3      1    3    0    1    1    1                                    50       4      5    4    3    5    5    5                             I-4     1       4      4    5    5    4    4    5                                    50       5      4    5    5    5    5    5                             I-5     1       0      1    2    1    0    1    1                                    50       3      4    5    4    3    4    4                             I-6     1       3      0    1    3    0    1    1                                    50       4      3    5    4    2    4    4                             I-7     1       2      0    1    1    0    1    0                                    50       4      3    5    4    2    4    3                             I-8     1       3      1    1    3    1    0    1                                    50       4      4    5    3    4    3    5                             ______________________________________                                         (Note)                                                                        A.r.: Amaranthus retroflexus                                                  B.p.: Bidens pilosa                                                           M.c.: Matricaria chamomilla                                                   S.n.: Solanum nigrum                                                          E.o.: Echinochloa oryzicola                                                   C.i.: Cyperus iria                                                            S.v.: Setaria viridis                                                    

We claim:
 1. AnN-substituted-3-[(2,3-dimethylmaleimido)-amino]benzenesulfonamidederivative of the formula (I): ##STR13## wherein R is C1, C₁ -C₃ alkylor C₁ -C₄ alkoxycarbonyl; Z is CH, X¹ is C1 or C₁ -C₃ alkoxyl; and X² isC₁ -C₃ alkyl or C₁ -C₃ alkoxyl.
 2. A derivative of claim 1, wherein, Ris C1, CH₃, COOCH₃ or COOC₂ H₅, X¹ is C1 or OCH₃, and X² is OCH₃.
 3. Aderivative of claim 1, wherein R is COOCH₃ or COOC₂ H₅, X¹ is OCH₃, andX² is CH₃ or OCH₃.
 4. A herbicidal composition comprising a herbicidallyeffective amount of anN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivative of claim 1 and an agronomically-acceptable vehicle ordiluent.
 5. A method for the control of monocotyledonous ordicotyledonous weeds on an agricultural or non-agricultural land, whichcomprises applying to the agricultural or non-agricultural land anN-substituted-3-[(2,3-dimethylmaleimido)amino]benzenesulfonamidederivative of claim 1 or a herbicidal composition comprising saidderivative.